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- W81193181 abstract "We study the electric double layer by combining the effects of ion finite size and ionic polarizability. At high surface potential, both mechanisms can cause saturation of the counter-ion concentration near a charged surface. The modified Grahame equation and differential capacitance are derived analytically for a general expression of a permittivity, epsilon(n), that depends on the local ion concentration, n, and under the assumption that the co-ions are fully depleted from the surface. The counter-ion concentration at saturation is found for any epsilon(n), and a criterion predicting which of the two mechanisms (steric vs. polarizability) is the dominant one is obtained. At low salinity, the differential capacitance as function of surface potential has two peaks (so-called camel-shape). Each of these two peaks is connected to saturation caused either by ion polarizability or by their finite size. Because these effects depend mainly on the counter-ion concentration at the surface proximity, for opposite surface-potential polarity either the cations or anions play the role of counter-ions, resulting in an asymmetric camel-shape. At high salinity, we obtain and analyze the crossover in the differential capacitance from a double-peak shape to a uni-modal one. Finally, several nonlinear models of the permittivity decrement are considered, and we predict that the dielectrophoretic saturation shifts to higher concentration than those obtained by the linear decrement model." @default.
- W81193181 created "2016-06-24" @default.
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- W81193181 date "2014-11-08" @default.
- W81193181 modified "2023-09-27" @default.
- W81193181 title "Differential capacitance of the electric double layer: The interplay between ion finite size and ionic polarizability" @default.
- W81193181 hasPublicationYear "2014" @default.
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